Herbicide containing substituted pyrazole derivative as active ingredient

ABSTRACT

A herbicide composition containing a substituted pyrazole derivative represented by the formula (I) set forth below as an active ingredient is disclosed, more particularly, a herbicide composition having a wide herbicidal spectrum, applicable in a small dosage with sufficient safety to certain important crops. The herbicide composition of the invention containing the substituted pyrazole derivative represented by the formula (I) as an active ingredient has a wide herbicidal spectrum, exerts an excellent herbicidal effect even in a small dose, and shows sufficient safety with respect to a number of important crops, such as rice, wheat and soybeans.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a substituted pyrazole derivativeuseful as a herbicide and to a herbicide composition containing thesubstituted pyrazole derivative as an active ingredient. Moreparticularly, the invention relates to a herbicide compositioncontaining as an active ingredient a substituted pyrazole derivativerepresented by the following formula (I), which has a wide herbicidalspectrum, can be applied in a small dose, shows sufficient safety tocertain important crops and is useful in fields of chemical industry andagriculture, particularly in a field of production of agriculturalchemicals.

2. Description of the Prior Art

In cultivation of important crops such as wheat, corn, soybean and rice,a great number of herbicides are employed at present. However, there aremany species of weeds to be controlled, and emergence of the weeds lastsover a long period of time. Therefore, most of the herbicides have aproblem that their herbicidal activity, herbicidal spectrum, residualeffectiveness and crop selectivity are not always satisfactory.

On this account, development of a novel herbicide composition exertingan excellent herbicidal effect even when applied in a small dose, havinga wide herbicidal spectrum and showing sufficient safety to certainimportant crops has been desired.

Under such circumstances as mentioned above, the present inventors havemade various studies, and as a result, they have found that asubstituted pyrazole derivative represented by the above formula (I) hasa wide herbicidal spectrum and exerts an excellent herbicidal effect andthat a herbicide composition containing the substituted pyrazolederivative as an active ingredient exerts an excellent herbicidal effecteven when it is applied in a small dose and shows sufficient safety tosome importance crops. Based on the finding, the present invention hasbeen accomplished.

In addition, it is also known that substituted pyrazole derivatives havefungicidal activity, and processes for synthesizing such derivatives aredescribed in Japanese Patent Laid-Open Publication No. 168063/1998 andEuropean Patent No. 0945437A1.

In the above publications, however, there is no description of theherbicidal activity of the substituted pyrazole derivatives at all, andalso in the prior art, it has not been found that the substitutedpyrazole has herbicidal activity.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide a herbicidecomposition containing a substituted pyrazole derivative represented bythe following formula (I) as an active ingredient, namely, a herbicidecomposition having a wide herbicidal spectrum, exerting an excellentherbicidal effect even when applied in a small dose and showingsufficient safety to some important crops.

The summary of the present invention is as follows.

(1) The herbicide composition according to the invention contains, as anactive ingredient, one or more substituted pyrazole derivativesrepresented by the following formula (1):

wherein X is R¹OOC, R¹HNOC, R¹R¹NOC, a cyano group or a 5-membered or6-membered aromatic heterocyclic group,

W is an alkylene group of 1 to 3 carbon atoms or NR¹,

R is a lower alkyl group of 1 to 4 carbon atoms or a lower haloalkylgroup of 1 to 4 carbon atoms,

A, B and D may be the same or different and are each a hydrogen atom, ahalogen atom or a group selected from the group consisting of R¹, R¹O,R¹S, R¹SO, R¹SO₂, (R¹)₂N, R¹OOC, R¹OR², R¹ON═CH, a cyano group, a nitrogroup, a lower alkenyl group of 2 to 4 carbon atoms, a lower alkynylgroup of 2 to 4 carbon atoms, a cycloalkyl group of 3 to 7 carbon atoms,Ph, PhCH₂, PhO, PhCH₂O, PhOR², PhS, PhCH₂S, PhSR², PhCH₂ON═CH, Naph andHet, with the proviso that there is no case where A, B and D arehydrogen atoms at the same time and there is no case where A, B and Dare aromatic groups or aromatic heterocyclic groups at the same time,

R¹ is a lower alkyl group of 1 to 4 carbon atoms or a lower haloalkylgroup of 1 to 4 carbon atoms,

R² is a lower alkylene group of 1 to 4 carbon atoms,

Ph is an unsubstituted or substituted phenyl group,

Naph is an unsubstituted or substituted naphthyl group, and

Het is an unsubstituted or substituted, 5-membered or 6-memberedaromatic heterocyclic group.

(2) The herbicide composition according to the invention preferablycontains as an active ingredient a substituted pyrazole derivative ofthe formula (I) wherein X is R¹OOC, W is a methylene group or anethylene group, R is a methyl group, A and B are each a hydrogen atom, ahalogen atom, R¹ or R¹S, and D is an unsubstituted or substituted phenylgroup (R¹ is a lower alkyl group of 1 to 4 carbon atoms or a lowerhaloalkyl group of 1 to 4 carbon atoms).

(3) The substituted pyrazole derivative contained in the herbicidecomposition described in the above (1) is preferably at least onecompound selected from the group consisting of the compounds No. 1 to 47enumerated in the later-described Table 1.

(4) The substituted pyrazole derivative contained in the herbicidecomposition described in the above (1) is more preferably a substitutedpyrazole derivative represented by the formula (I):

wherein X is R¹OOC, R¹HNOC or R¹R¹NOC,

W is a lower alkylene group of 1 to 3 carbon atoms,

R is a lower alkyl group of 1 to 4 carbon atoms,

A and B are each a hydrogen atom, a halogen atom, R¹ or R¹S,

D is a phenyl group, a naphthyl group or a 5-membered or 6-memberedaromatic heterocyclic group (these groups may be unsubstituted or mayhave a substituent), and

R¹ is a lower alkyl group of 1 to 4 carbon atoms or a lower haloalkylgroup of 1 to 4 carbon atoms.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The herbicide according to the invention is described in detailhereinafter.

Substituted Pyrazole Derivatives

The substituted pyrazole derivative that is an active ingredient of theherbicide of the invention is represented by the following formula (I).

In the formula (I), X is R¹OOC, R¹HNOC, R¹R¹NOC, a cyano group or a5-membered or 6-membered aromatic heterocyclic group. R¹ is a loweralkyl group of 1 to 4 carbon atoms or a lower haloalkyl group of 1 to 4carbon atoms, and these groups may be straight-chain or branched. Thehaloalkyl group means an alkyl group substituted with one or morehalogen atoms which are the same or different.

Examples of R¹OOC include methoxycarbonyl group, ethoxycarbonyl group,propoxycarbonyl group and butoxycarbonyl group. Of these,methoxycarbonyl group is preferable.

Examples of R¹HNOC include methylaminocarbonyl group andethylaminocarbonyl group. Examples of R¹R¹NOC includedimethylaminocarbonyl group, diethylaminocarbonyl group andethylmethylcarbonyl group. Of these, methylaminocarbonyl group ispreferable.

The 5-membered or 6-membered aromatic heterocyclic group is a 5-memberedor 6-membered aromatic heterocyclic compound residue containing N, O orS atom as a cyclic atom, and examples of such groups include 2-pyridylgroup, 3-pyridyl group, 4-pyridyl group, 2-furyl group, 3-furyl group,2-thienyl group and 3-thienyl group.

In the formula (I), W is an alkylene group of 1 to 3 carbon atoms orNR¹, and examples of such groups include methylene group, ethylenegroup, trimethylene group, methylamino group and ethylamino group. Ofthese, methylene group is preferable.

In the formula (I), R is a lower alkyl group of 1 to 4 carbon atoms or alower haloalkyl group of 1 to 4 carbon atoms and may be straight-chainor branched. Examples of such groups include methyl group, fluoromethylgroup and difluoromethyl group. Of these, methyl group is preferable.

In the formula (I), A, B and D may be the same or different and are eacha hydrogen atom, a halogen atom or a group selected from the groupconsisting of R¹, R¹O, R¹S, R¹SO, R¹SO₂, (R¹)₂N, R¹OOC, R¹OR², R¹ON═CH,a cyano group, a nitro group, a lower alkenyl group of 2 to 4 carbonatoms, a lower alkynyl group of 2 to 4 carbon atoms, a cycloalkyl groupof 3 to 7 carbon atoms, Ph, PhCH₂, PhO, PhCH₂O, PhOR², PhS, PhCH₂S,PhSR², PhCH₂ON═CH, Naph and Het, but there is no case where A, B and Dare hydrogen atoms at the same time, and there is no case where A, B andD are aromatic groups or aromatic heterocyclic groups at the same time.

R¹ is the same group as described above, R² is a lower alkylene group of1 to 4 carbon atoms, Ph is an unsubstituted or substituted phenyl group,NapH is an unsubstituted or substituted naphthyl group, and Het is anunsubstituted or substituted, 5-membered or 6-memebered aromaticheterocyclic group.

Examples of the halogen atoms reperesented by A, B and D includefluorine atom, chlorine atom, bromine atom and iodine atom. Examples ofR¹ include methyl group, ethyl group, propyl group, butyl group,fluoromethyl group, difluoromethyl group and their isomeric groups.Examples of R² include methylene group, ethylene group, trimethylenegroup, tetramethylene group and their isomeric groups.

Examples of R¹O include methoxy group, ethoxy group, propoxy group andbutoxy group. Of these, methoxy group is preferable.

Examples of R¹S include methylthio group, ethylthio group, propylthiogroup and butylthio group. Of these, methylthio group is preferable.

Examples of R¹SO include methylsulfinyl group, ethylsulfinyl group,propylsulfinyl group and butylsulfinyl group. Of these, methylsulfinylgroup is preferable.

Examples of R¹SO₂ include methylsulfonyl group, ethylsulfonyl group,propylsulfonyl group and butylsulfonyl group. Of these, methylsulfonylgroup is preferable.

Examples of (R¹)₂N include dimethylamino group, diethylamino group,dipropylamino group, dibutylamino group and ethylmethylamino group.

Examples of R¹OOC include methoxycarbonyl group, ethoxycarbonyl group,propoxycarbonyl group and butoxycarbonyl group. Of these,methoxycarbonyl group is preferable.

Examples of R¹OR² include methoxymethyl group, ethoxymethyl group,propoxymethyl group and butoxymethyl group.

Examples of R¹ON═CH include methoxyiminomethyl group.

The lower alkenyl group of 2 to 4 carbon atoms may be straight-chain orbranched, and examples of such groups include vinyl group, propenylgroup, butenyl group and their isomeric groups.

The lower alkynyl group of 2 to 4 carbon atoms may be straight-chain orbranched, and examples of such groups include ethynyl group, propynylgroup, butynyl group and their isomeric groups.

Examples of the cycloalkyl groups of 3 to 7 carbon atoms includecyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl groupand cycloheptyl group. Of these, cyclopropyl group is preferable.

Ph represented by A, B and D is a phenyl group, a 1- to 5-substitutedphenyl group substituted with a halogen atom or a group selected fromthe group consisting of R¹, R¹O, R¹S, R¹SO, R¹SO₂, (R¹)₂N, R¹OOC, R¹OR²,R¹ON═CH, a cyano group, a nitro group, a lower alkenyl group of 2 to 4carbon atoms, a lower alkynyl group of 2 to 4 carbon atoms and acycloalkyl group of 3 to 7 carbon atoms, or a 1-substituted phenyl groupsubstituted with a group selected from the group consisting of Ph,PhCH₂, PhO, PhCH₂O, PhCH₂ON═CR¹, PhCO and Het—O.

Het is a 5-membered or 6-membered aromatic heterocyclic group, or a5-membered or 6-membered aromatic heterocyclic group having a cyclicring wherein two of substituents R¹ and/or R¹O are present at thevicinal positions to form the cyclic structure together with the benzenering. Examples of such groups include 2-pyridyl group, 3-pyridyl group,4-pyridyl group, 2-furyl group, 3-furyl group, 2-thienyl group,3-thienyl group, 1,3-benzodioxole-4-yl group,2,2-dimethyl-1,3-benzodioxole-4-yl group and2,2-difluoro-1,3-benzodioxole-4-yl group.

Naph represented by A, B and D is a naphthyl group or a 1- or2-substituted naphthyl group substituted with a halogen atom, R¹ or R¹O.

Het represented by A, B and D may be a 1- to 4-substituted 5-membered or1- to 4-substituted 6-membered aromatic heterocyclic group substitutedwith an alkyl group of 1 to 4 carbon atoms or a halogen atom, other thanthe above Het group. Examples of such groups include 2-methyl-6-pyridylgroup, 3,5-dimethyl-2-furyl group, 3,5-dimethyl-2-thienyl group,N-methyl-3-pyrrolyl group and 2,4-dimethyl-5-thiazoyl group.

Preferred examples of the groups represented by A, B and D includephenyl group, methylphenyl group, chlorophenyl group, dichlorophenylgroup, 3-[1-(chlorobenzyloxyimino)-ethyl]phenyl group,3-(benzyloxy)phenyl group, 3-(methylbenzyloxy)phenyl group,3-(chlorobenzyloxy)phenyl group, 3-(cyanobenzyloxy)phenyl group,3-(dimethylbenzyloxy)phenyl group, 3-(dichlorobenzyloxy)phenyl group,3-(pyridylmethoxy)phenyl group, 3-(benzoyloxy)phenyl group,3-(chlorobenzoyloxy)phenyl group, 3-(6-chloropyrimidine-4-yloxy)phenylgroup, 3-(6-methoxypyrimidine-4-yloxy)phenyl group,3-[6-(2-methylphenoxy)-pyrimidine-4-yloxy]phenyl group,[6-(2-cyanophenoxy)pyrimidine-4-yloxy]phenyl group,3-(6-chloro-5-nitropyrimidine-4-yloxy)phenyl group,3-(2-benzothiazolyloxy)phenyl group, benzyl group, phenoxymethyl group,methylphenoxymethyl group, phenylthiomethyl group,methylphenylthiomethyl group, 1-phenoxyethyl group,1-(methylphenoxy)ethyl group, 1-phenylthioethyl group,1-(methylphenylthio)ethyl group, 1,3-benzodioxole-4-yl group,2,2-dimethyl-1,3-benzodioxole-4-yl group,2,2-difluoro-1,3-benzodioxole-4-yl group, phenoxy group, 2-methylphenoxygroup, 3-methylphenoxy group, 4-methylphenoxy group, 2-chlorophenoxygroup, 3-chlorophenoxy group, 4-chlorophenoxy group,2-trifluoromethylphenoxy group, 2,5-dimethylphenoxy group,2,5-dichlorophenoxy group, 2chloro-5-trifluoromethylphenoxy group,phenylthio group, 2-methylphenylthio group, 3-methylphenylthio group,4-methylphenylthio group, 2-chlorophenylthio group, 3-chlorophenylthiogroup, 4-chlorophenylthio group, 2-trifluoromethylphenylthio group,2,5-dimethylphenylthio group, 2,5-dichlorophenylthio group,2-chloro-5-trifluoromethylphenylthio group, benzyloxy group,2-methylbenzyloxy group, 3-methylbenzyloxy group, 4-methylbenzyloxygroup, 2-chlorobenzyloxy group, 3-chlorobenzyloxy group,4-chlorobenzyloxy group, 2-trifluoromethylbenzyloxy group,2,5-dimethylbenzyloxy group, 2,5-dichlorobenzyloxy group,2-chloro-5-trifluoromethylbenzyloxy group, benzylthio group,2-methylbenzylthio group, 3-methylbenzylthio group, 4-methylbenzylthiogroup, 2-chlorobenzylthio group, 3-chlorobenzylthio group,4-chlorobenzylthio group, 2-trifluoromethylbenzylthio group,2,5-dimethylbenzylthio group, 2,5-dicholobenzylthio group,2-chloro-5-trifluoromethylbenzylthio group, benzyloxyiminomethyl group,2-methylbenzyloxyiminomethyl group, 3-methylbenzyloxyiminomethyl groupand 4-methylbenzyloxyiminomethyl group.

Specific examples of the substituted pyrazole derivatives represented bythe formula (I) include those enumerated in Table 1, but the substitutedpyrazole derivatives employable in the invention are not restricted tothose examples. The compound numbers in the table are referred to alsoin the later-described working examples. In the table, Me denotes amethyl group, Et denotes an ethyl group, Pr denotes a propyl group, andPh denotes an unsubstituted phenyl group (only in Table 1).

Physical property values of the compounds enumerated in Table 1 are setforth in Table 2.

TABLE 1

Compound No. A B D W X R 1 H H Ph CH₂ CO₂Me Me 2 Me H Ph CH₂ CO₂Me Me 3Me H 3-Me—Ph CH₂ CO₂Me Me 4 Me H 2-Cl—Ph CH₂ CO₂Me Me 5 Me H2,5-(Me)₂—Ph CH₂ CO₂Me Me 6 Me H 2,3-(Cl)₂—Ph CH₂ CO₂Me Me 7 Me H2,4-(Cl)₂—Ph CH₂ CO₂Me Me 8 Me H 2,5-(Cl)₂—Ph CH₂ CO₂Me Me 9 Me H2,6-(Cl)₂—Ph CH₂ CO₂Me Me 10 Me H 3,4-(Cl)₂—Ph CH₂ CO₂Me Me 11 Me H3,5-(Cl)₂—Ph CH₂ CO₂Me Me 12 Me Cl Ph CH₂ CO₂Me Me 13 H Me Ph CH₂ CO₂MeMe 14 H Me 4-F—Ph CH₂ CO₂Me Me 15 H Cl Ph CH₂ CO₂Me Me 16 H Cl 3-OMe—PhCH₂ CO₂Me Me 17 Me Cl 3-Me—Ph CH₂ CO₂Me Me 18 Me Cl 2-Cl—Ph CH₂ CO₂Me Me19 Me Cl 2,5-(Me)₂—Ph CH₂ CO₂Me Me 20 Me Cl 2,3-(Cl)₂—Ph CH₂ CO₂Me Me 21Me Cl 2,4-(Cl)₂—Ph CH₂ CO₂Me Me 22 Me Cl 2,5-(Cl)₂—Ph CH₂ CO₂Me Me 23 MeCl 2,6-(Cl)₂—Ph CH₂ CO₂Me Me 24 Me Cl 3,4-(Cl)₂—Ph CH₂ CO₂Me Me 25 Me Cl3,5-(Cl)₂—Ph CH₂ CO₂Me Me 26 Me Br 3-Me—Ph CH₂ CO₂Me Me 27 Me Br 2-Cl—PhCH₂ CO₂Me Me 28 Me Br 2,5-(Me)₂—Ph CH₂ CO₂Me Me 29 Me Br 2,3-(Cl)₂—PhCH₂ CO₂Me Me 30 Me Br 2,4-(Cl)₂—Ph CH₂ CO₂Me Me 31 Me Br 2,5-(Cl)₂—PhCH₂ CO₂Me Me 32 Me Br 3,5-(Cl)₂—Ph CH₂ CO₂Me Me 33 Me Me Ph CH₂ CO₂Me Me34 Me Me 3-Cl—Ph CH₂ CO₂Me Me 35 Me Me 4-Cl—Ph CH₂ CO₂Me Me 36 Et H PhCH₂ CO₂Me Me 37 SMe H Ph CH₂ CO₂Me Me 38 SMe H 3-Cl—Ph CH₂ CO₂Me Me 39Et Cl Ph CH₂ CO₂Me Me 40 Pr Cl 3-Cl—Ph CH₂ CO₂Me Me 41 SMe Cl Ph CH₂CO₂Me Me 42 SMe Cl 3-Cl—Ph CH₂ CO₂Me Me 43 Et Br Ph CH₂ CO₂Me Me 44 SMeBr Ph CH₂ CO₂Me Me 45 Cl Me Ph CH₂ CO₂Me Me 46 Br Me Ph CH₂ CO₂Me Me 47H Me Ph C₂H₄ CO₂Me Me

TABLE 2 Compound No. Physical properties δ value (ppm, solvent: CDCI₃,internal standard substance; TMS) 1 oil 3.55(3H, S), 3.92(3H, S),5.02(2H, S), 6.50(1H, d, J=4.5 Hz), 7.20˜7.95(7H, m) 2 oil 2.36(3H, s),3.69(3H, s), 3.91(3H, s), 4.88(2H, s), 6.23(1H, s), 7.10˜7.90(6H, m) 3mp 68˜70° C. 4 mp 91˜92° C. 5 oil 2.29(3H, s), 2.37(3H, s), 3.70(3H, s),3.90(3H, s), 4.89(2H, s), 6.08(1H, s), 6.80˜7.60(4H, m) 6 oil 2.39(3H,s), 3.69(3H, s), 3.89(3H, s), 4.90(2H, s), 6.47(1H, s), 7.00˜7.80(4H, m)7 mp 97˜99° C. 8 oil 2.39(3H, s), 3.70(3H, s), 3.92(3H, s), 4.90(2H, s),6.51(1H, s), 7.00˜7.90(4H, m) 9 mp 121˜123° C. 10 mp 74˜76° C. 11 mp114˜116° C. 12 mp 69˜71° C. 13 oil 2.19(3H, s), 3.74(3H, s), 3.93(3H,s), 4.96(2H, s), 7.20˜7.93(7H, m) 14 oil 2.19(3H, s), 3.73(3H, s),3.82(3H, s), 4.81(2H, s), 6.80˜7.84(6H, m) 15 oil 3.16(2H, s), 3.88(3H,s), 4.91(2H, s), 7.16˜7.95(7H, m) 16 oil 3.65(3H, s), 3.88(3H, s),3.92(3H, s), 5.02(2H, s)6.77˜7.58(5H, m) 17 mp 70˜72° C. 18 oil 2.10(3H,s), 2.27(3H, s), 3.76(3H, s), 3.83(3H, s), 4.80(2H, s), 7.10˜7.80(6H, m)19 oil 2.24(3H, s), 2.30(3H, s), 2.35(3H, s), 3.70(3H, s), 3.89(3H, s),4.90(2H, s), 6.80˜7.60(4H, m) 20 oil 2.36(3H, s), 3.70(3H, s), 3.90(3H,s), 4.90(2H, s), 7.10˜7.60(4H, m) 21 oil 2.36(3H, s), 3.70(3H, s),3.90(3H, s), 4.90(2H, s), 7.10˜7.60(4H, m) 22 oil 2.33(3H, s), 3.64(3H,s), 3.38(3H, s), 4.90(2H, s), 7.17˜7.41(4H, m) 23 mp 107˜108° C. 24 mp115˜117° C. 25 mp 98˜110° C. 26 oil 2.47(6H, s), 3.67(3H, s), 3.86(3H,s), 4.88(2H, s), 7.00˜7.80(4H, m) 27 oil 2.16(3H, s), 2.38(3H, s),3.70(3H, s), 3.89(3H, s), 4.95(2H, s), 7.05˜7.60(5H, m) 28 oil 2.22(3H,s), 2.30(3H, s), 2.37(3H, s), 3.70(3H, s), 3.89(3H, s), 4.92(2H, s),6.90˜7.60(4H, m) 29 oil 2.35(3H, s), 3.66(3H, s), 3.84(3H, s), 4.90(2H,s), 7.05˜7.60(4H, m) 30 oil 2.37(3H, s), 3.70(3H, s), 3.89(3H, s),4.93(2H, s), 7.10˜7.70(4H, m) 31 oil 2.38(3H, s), 3.70(3H, s), 3.90(3H,s), 4.94(2H, s), 7.10˜7.60(4H, m) 32 mp 102˜105° C. 33 oil 2.10(3H, s),2.27(3H, s), 3.70(3H, s), 3.90(3H, s), 4.88(2H, s), 7.00˜7.80(6H, m) 34mp 98˜100° C. 35 oil 2.05(3H, s), 2.25(3H, s), 3.65(3H, s), 3.86(3H, s),4.83(2H, s), 7.10˜7.70(5H, m) 36 oil 1.30(3H, t, J=7.5 Hz), 2.75(2H, q,J=7.5 Hz), 3.68(3H, s), 3.89(3H, s), 4.88(2H, s), 6.27(1H, s),7.00˜7.90(6H,m) 37 oil 2.48(3H, s), 3.71(3H, s), 3.90(3H, s), 5.07(2H,s), 6.55(1H, s), 7.10˜7.90(6H, m) 38 oil 2.47(3H, s), 3.71(3H, s),3.92(3H, s), 5.06(2H, s), 6.52(1H, s), 7.10˜7.80(5H, m) 39 oil 1.21(3H,t, J=7.7 Hz), 2.81(2H, q, J=7.7 Hz), 3.64(3H, s), 3.84(3H, s), 4.85(2H,s), 7.10˜8.00(6H, m) 40 oil 0.89˜1.95(5H, m), 3.69(3H, s), 3.89(3H, s),5.03(2H, s), 7.17˜7.40(2H, m), 7.54(1H, s), 7.64˜7.81(2H, m) 41 oil2.41(3H, s), 3.68(3H, s), 3.87(3H, s), 5.13(2H, s), 7.20˜8.00(6H, m) 42oil 2.43(3H, s), 3.70(3H, s), 3.91(3H, s), 5.15(2H, s), 7.20˜8.00(5H, m)43 oil 1.19(3H, t, J=7.6 Hz), 2.82(2H, q, J=7.6 Hz), 3.65(3H, s),3.82(3H, s), 4.87(2H, s), 7.10˜8.00(6H, m) 44 oil 2.42(3H, s), 3.70(3H,s), 3.88(3H, s), 5.18(2H, s), 7.20˜8.00(6H, m) 45 resin 1.89(3H, s),3.70(3H, s), 3.88(3H, s), 4.64(2H, s), 7.10˜8.10(6H, m) 46 resin2.15(3H, s), 3.75(3H, s), 3.97(3H, s), 5.29(2H, s), 7.10˜8.00(6H, m) 47oil 2.20(3H, s), 2.78(2H, t, J=6.3 Hz), 3.66(3H, s), 3.70(3H, s),4.17(2H, t, J=6.3 Hz), 7.16˜7.77(7H, m)

Preparation of Substituted Pyrazole Derivatives

The substituted pyrazole derivative represented by the formula (I) canbe prepared in accordance with the processes described in the aforesaidpublications (Japanese Patent Laid-Open Publication No. 168063/1998,European Patent No. 0945437A1). For example, a substituted pyrazolederivative of the formula (I) wherein X is R¹OOC, W is alkylene of 1 to3 carbon atoms, R is lower alkyl of 1 to 4 carbon atoms, and D is Ph isfavorably prepared by reacting an alkanoic acid ester derivativerepresented by the following formula (II) (wherein n is 1 to 3) (i.e.,acetic acid ester derivative, propionic acid ester derivative orbutanoic acid ester derivative) with a formylating agent in the presenceof a base and a solvent, followed by the reaction with an alkylatingagent in the presence of a base.

In the reaction of the alkanoic acid ester represented by the formula(II) with the formylating agent, formic acid esters and formic acidamides are used as the formylating agent. As the base, sodium hydride,alkyllithiums, lithium amides and the like are used.

With regard to the amounts of the agents used in the reaction, theformylating agent is used in an amount of about 1 to 10 equivalents andthe base is used in an amount of 1 to 2 equivalents, based on 1equivalent of the alcanoic acid ester derivative represented by theformula (II). In the above reaction, solvents, such as ethers and acidamides, are usually used.

In the reaction with the alkylating agent, alkyl halides and sulfuricacid esters are used as the alkylating agent. As the base, tertiaryamines such as pyridine, inorganic bases such as sodium hydride, and thelike are used.

With regard to the amounts of the agents used in the reaction, thealkylating agent is used in an amount of about 1 to 2 equivalents andthe base is used in an amount of about 1 to 2 equivalents, based on 1equivalent of the formylated compound. In the above reaction, solvents,such as ethers, acid amides and ketones, are usually used. After thereaction, the reaction mixture may be post-treated by a conventionalmethod, and if necessary, purification is carried out, whereby thedesired substituted pyrazole derivative is obtained.

The alkanoic acid ester derivative represented by the formula (II) isobtained by reacting a pyrazole derivative represented by the followingformula (III):

wherein A and B represent the same as the above defined symbolsrespectively.

with a haloacetic acid ester, a halopropionic acid ester or ahalobutanoic acid ester represented by the following formula (IV):

Z—CH₂(CH₂)_(n)CO₂R¹  (IV)

wherein Z is a halogen atom, R¹ is a lower alkyl group of 1 to 4 carbonatoms, and n is 0, 1 or 2,

in the presence of a base.

Details of the process for preparing the pyrazole derivative representedby the formula (III) are as described in the aforesaid publications.

Herbicide Compositions Containing Substituted Pyrazole Derivative asActive Ingredient

The herbicide composition according to the invention is characterized bycontaining the above-mentioned substituted pyrazole derivative as anactive ingredient. The composition exerts an excellent herbicidal effecteven in a small dose, with a wide herbicidal spectrum, showingsufficient safety to certain important crops.

This is attributable to the properties of the substituted pyrazolederivative, an active ingredient of the herbicide composition of theinvention. The herbicidal spectrum of the substituted pyrazolederivative and the crop selectivity thereof are described below indetail.

Herbicidal Activity of Substituted Pyrazole Derivative

(A) Herbicidal Spectrum

(A1) Herbicidal Spectrum in an Upland Field

In any treatment among soil treatment, soil incorporation treatment andfoliage treatment, the substituted pyrazole derivative for use in theinvention has high herbicidal activity as an upland field or non-cropland herbicide even in a small dose against various species of uplandfield weeds, for example, broad leaf weeds, specifically, Solanaceaeweeds, such as Solanum nigrum and Datura stramonium, Malvaceae weeds,such as Abutilon theophrasti and Sida spinosa, Convolvulaceae weeds,such as Ipomoea spps. (e.g., Ipomoea purpurea) and Calystegia spps.,Amaranthaceae weeds, such as Amaranthus lividus and Amaranthusretroflexus, Compositae weeds, such as Xanthium pensylvanicum, Ambrosiaartemisiaefolia, Helianthus annuus, Galinsoga ciliata, Cirsium arvense,Senecio vulgaris, Erigeron annus and Matricaria inodora, Cruciferaeweeds, such as Rorippa indica, Sinapis arvensis and CapsellaBursapastoris, Polygonaceae weeds, such as Polygonum Blumei andPolygonum convolvulus, Portulacaceae weeds, such as Portulaca oleracea,Chenopodiaceae weeds, such as Chenopodium album, Chenopodium ficifoliumand Kochia scoparia, Caryophyllaceae weeds, such as Stellaria media,Scrophulariaceae weeds, such as Veronica persica, Commelinaceae weeds,such as Commelina communis, Labiatae weeds, such as Lamium amplexicauleand Lamium purpureum, Euphorbiaceae weeds, such as Euphorbia supina andEuphorbia maculata, Rubiaceae weeds, such as Galium spurium and Rubiaakane, Violaceae weeds, such as viola mandshurica, and Laguminosaeweeds, such as Sesbania exaltata and Cassia obtusifolia; and otherweeds, specifically, Gramineous weeds, such as Sorgham bicolor, Panicumdichotomiflorum, Sorghum halepense, Echinochloa crus-galli var.crus-galli, Echindchloa crus-galli var. praticola, Echinochloa utilis,Digitaria adscendens, Avenafatua, Eleusine indica, Setaria viridis,Alopecurus aegualis and Poa annua, and Cyperaceous weeds, such asCyperus rotundus (Cyperus esculentus).

Further, weeds over a wide range, such as those which emerge in mowedfield, non-cultivation land, land under perennial crops, pasture, lawn,railway side, vacant lot, forest, farm load, levee and other non-croplands, can be removed.

(A2) Herbicidal Spectrum in an Paddy Field

In any treatment of water-logged soil treatment and foliage treatment,the substituted pyrazole derivative for use in the invention has highherbicidal activity as a paddy field herbicide even in a small doseagainst various species of paddy field weeds, specifically, Alismataceaeweeds, such as Alisma canaliculatum, Sagittaria trifolia and Sagittariapygmaea, Cyperaceous weeds, such as Cyperus difformis, Cyperusserotinus, Scirpus juncoides, Eleocharis kuroguwai and Eleocharisacicularis, Scrophulariaceae weeds, such as Lindernia pyxidaria,Pontederiaceae weeds, such as Monochoria vaginalis, Potamogetonaceaeweeds, such as Potamogeton distinctus, Umbelliferae weeds, such asOenanthe javanica, Lythraeae weeds, such as Rotala indica and Ammanniamultiflora, Elantinaceae weeds, such as Elatine triandra, andGraminaceous weeds, such as Echinochloa oryzicola, Echinochloacrus-galli var. formosensis and Echinochloa crus-galli var. crus-galli.

(A3) Effect on Aquatic Plants

The substituted pyrazole derivative for use in the invention exerts aneffect on algae, such as blue-green algae, and aquatic weeds, such asEichhornia crassipes, which emerge in creeks, canals, lakes, marshes,ponds, etc.

(B) Crop Selectivity

(B1) Crop Selectivity in an Upland Field

The substituted pyrazole derivative for use in the invention shows highsafety to main crops, such as Oryza sativa, Triticum aestivum, Hordeumvulgare, Sorghum bicolor, Arachis hypogaea, Zea mays, Glycine max,Gossypium spp. and Beat vulgaris, and garden crops, such as flowers,ornamental plants and vegetable crops.

(B2) Crop Selectivity (Paddy Rice)

The substituted pyrazole derivative for use in the invention does notpose a significant chemical hazard to transplantation paddy rice ordirect-sowing paddy rice.

(B3) Crop Selectivity (Lawn Grass)

The substituted pyrazole derivative for use in the invention shows highsafety to lawn grasses, such as Japanese lawn grass and Western lawngrass.

Ingredients of the Herbicide Composition

The herbicide composition of the invention contains, as an activeingredient, the substituted pyrazole derivative having such a wideherbicidal spectrum and such a crop selectivity as described above.Although the content of the substituted pyrazole derivative can bechanged according to the conditions such as formulation of the herbicidecomposition and application method thereof and is not specificallyrestricted, it is in the range of usually about 0.01 to 90% by weight.

The herbicide composition of the invention may contain one or more kindsof the substituted pyrazole derivatives as active ingredients.

The herbicide composition of the invention may further contain, inaddition to the substituted pyrazole derivative, one or plural plantprotecting agents, such as fungicides, insecticides, herbicides,nematicides, acaricides, bactericides, chemical injury decreasingagents, plant growth regulators, fertilizers and soil improvers, asmixed chemicals.

By the addition of such other ingredients, particularly other herbicidalactive ingredients (referred to as “other herbicides” hereinafter), itbecomes possible to reduce the total dose of the herbicide composition.Moreover, besides labor-saving, widening of a herbicidal spectrum andmuch higher herbicidal effect can be expected owing to the synergisticaction of the mixed chemicals. The herbicide composition may containplural kinds of other herbicides at the same time.

Examples of the other herbicides include those described in a catalog ofFarm Chemical Handbook (Meister Publishing Company) (1997), SHIBUYAINDEX (8th edition) (1999), The Pesticide Manual (British cropprotection council) 12th edition (2000), and Herbicide researchconspectus (Hakuyu-sha), such as atrazine, cyanazine, dimethametryn,metribuzin, prometryn, simazine, simetryn, chlortoluron, diuron,daimuron, fluometuron, isoproturon, linuron, methabenzthiazuron,amicarbazone, bromoxynil, ioxynil, ethalfluralin, pendimethalin,trifluralin, acifluorfen, acifluorfen-sodium, bifenox, chlomethoxynil,fomesafen, lactofen, oxadiazon, oxadiargyl, oxyfluorfen,carfentrazone-ethyl, flumiclorac-pentyl, flumioxazine,fluthiacet-methyl, sulfentrazone, thidiazimin, azafenidin,pyraflufen-ethyl, cinidon-ethyl, difenzoquat, diquat, paraquat, 2,4-D,2,4-DB, DCPA, MCPA, MCPB, clomeprop, clopyralid, dicamba, dithiopyr,fluroxypyr, mecoprop, naploanilide, phenothiol, quinclorac, triclopyr,thiazopyr, acetochlor, alachlor, butachlor, diethatyl-ethyl,metolachlor, pretilachlor, propachlor, bensulfuron-methyl,chlorsulfuron, chlorimuron-ethyl, halosulfuron-methyl,metsulfuron-methyl, nicosulfuron, primisulfuron-methyl,pyrazosulfuron-ethyl, sulfometuron-ethyl, thifensulfuron-methyl,triasulfuron, tribenuron-methyl, oxasulfuron, azimsulfuron,cloransulam-methyl, cyclosulfamuron, flumetsulam, florasulam,flupyrsulfuron, flazasulfuron, imazosulfuron, metosulam, diclosulam,prosulfuron, rimsulfuron, triflusulfuron-methyl, ethoxysulfuron,sulfosulfuron, flucarbazone-sodium, procarbazone-sodium (MKH-6561),imazamethabenz-methyl), imazapyr, imazaquin, imazethapyr, imazameth,imazamox, bispyribac-sodium, pyriminobac-methyl, pyrithiobac-sodium,alloxydim-sodium, clethodim, sethoxydim, tralkoxydim, tepraloxydim,profoxydim (BAS-625H), diclofop-methyl, fenoxaprop-ethyl,fenoxaprop-p-ethyl, fluazifop-butyl, fluazifop-p-butyl,haloxyfop-methyl, quizalofop-p-ethyl, cyhalofop-butyl,clodinafop-propargyl, benzofenap, clomazone, diflufenican, norflurazone,pyrazolate, pyrazoxyfen, picolinafen, beflubutamid, flurtamone,isoxaflutole, sulcotrione, benzobicyclon, mesotrione,glufosinate-ammonium, glyphosate, bentazone, benthiocarb, bromobutide,butamifos, butylate, dimepiperate, dimethenamid, DSMA, EPTC, esprocarb,isoxaben, mefenacet, molinate, MSMA, piperophos, pyributicarb,prosulfocarb, propanil, pyridate, triallate, cafenstrol, flupoxam,flufenacet, diflufenzopyr, triaziflam, pentoxazone, indanofan,metobenzuron, oxaziclomefone and fentrazamide.

Although the mixing ratio between the substituted pyrazole derivativeand other herbicides in the herbicide composition of the inventionvaries depending upon the types of active ingredients of otherherbicides, etc., it is preferably in the range of usually 1:0.01 to1:10, by weight.

Formulation

There is no specific limitation on the formulation of the herbicidecomposition of the invention, as far as the composition contains thesubstituted pyrazole derivative as an active ingredient. For example, inthe practical application as a herbicide, the substituted pyrazolederivative may be used just as it is, but by the addition of additivesgenerally used for formulating, such as carriers, surface active agents,dispersants and adjuvants, the herbicide composition can be used as anyof generally adoptable formulations of agricultural chemicals, such aswettable powders, granules, powders, emulsions, water-soluble powders,suspensions and flowables.

Examples of the solid carriers or diluents include plant substances,fibrous materials, synthetic plastic powders, clays (e.g., kaolin,bentonite, terra abla), talc or inorganic materials (pumice, powderedsulfur), and chemical fertilizers. Examples of the liquid carriers ordiluents include water, alcohols, ketones, ethers, aromatichydrocarbons, aliphatic hydrocarbons, esters, nitrites, amides(N,N-dimethylformamide, dimethyl sulfoxide), and halogenatedhydrocarbons.

Examples of the surface active agents include alkylsulfuric acid esters,alkyl sulfonates, polyethylene glycol ethers and polyhydric alcoholesters. Examples of the spreaders or the dispersants include casein,gelatin, starch, caboxymethyl cellulose, gum arabic, alginic acid,lignin, bentonite, polyvinyl alcohol, pine oil, molasses and agar.

Examples of the stabilizers include isopropylphosphate mixture,tricresyl phosphate, tall oil, epoxy oil, surface active agents, fattyacids and the esters thereof.

The concentration of the active ingredient in the herbicide compositionof the invention can be variously changed according to the formulationas described above, and in case of wettable powders, the activeingredient concentration is desirable to be in the range of preferably 5to 90% by weight, more preferably 10 to 85% by weight. In case ofemulsions, the active ingredient concentration is desirable to be in therange of preferably 3 to 70% by weight, more preferably 5 to 60% byweight, and in case of granules, the active ingredient concentration isdesirable to be in the range of preferably 0.01 to 50% by weight, morepreferably 0.05 to 40% by weight.

Also when the herbicide composition of the invention contains theaforesaid other herbicides, the formulation is not specificallyrestricted, and for example, it is possible that the substitutedpyrazole derivative and the active ingredient of other herbicides areeach previously mixed with a solid carrier, a liquid carrier, a surfaceactive agent or other formulation adjuvants to prepare an emulsion, awettable powder, a suspension, a water-soluble granule, a water-solublepowder, an aqueous solution, a water-dispersible granule or the like,followed by mixing. It is also possible that the substituted pyrazolederivative is mixed with other herbicides and then the admixture ismixed with a solid carrier, a liquid carrier, a surface active agent orother formulation adjuvants to prepare an emulsion, a wettable powder, asuspension, a granule, a concentrated emulsion, a water-dispersiblegranule or the like. In the resulting formulation, the substitutedpyrazole derivative and other herbicides are desirably contained at thetotal amount of preferably 0.5 to 80% by weight, more preferably 1.5 to70% by weight.

Application Method

When the herbicide composition of the invention is applied as aherbicide, plants can be directly treated with the composition byspraying, dispersing, spreading or coating. Otherwise, the soil aroundthe plants, upland field, paddy field, lawn, etc. can be treated withthe composition by application or incorporation.

In case of, for example, a wettable powder or an emulsion, the powder orthe emulsion is diluted with water to give a suspension or a diluteemulsion of a prescribed concentration, and the suspension or the diluteemulsion can be sprayed or incorporated before or after sprouting of theobjective weeds. In case of a granule, the granule can be directlyapplied or incorporated as such before or after sprouting of theobjective weeds. When the herbicide composition of the invention ispractically applied as a herbicide, the composition can be used in sucha proper amount that the amount of the active ingredient becomes usuallynot less than 0.1 g based per hectare.

When the herbicide composition of the invention is practically used as aherbicide, the amount of the composition used is desired to be in therange of usually 10 g to 8000 g, preferably 10 g to 2000 g per hectare,though it varies with the meteorological conditions, formulation types,application times, application methods, soil conditions, objectivecrops, weeds to be controlled, etc. In case of an emulsion, a wettablepowder, a suspension, a concentrated emulsion, a water-dispersiblegranule, a liquid or the like, it is preferable to dilute a given amountof the formulation with usually 10 to 100 liters of water or wateroptionally containing adjuvants such as a spreader, prior toapplication. In case of a granule, a certain suspension or a certainliquid, it is preferable to apply it as such without diluting. Examplesof the adjuvants include the surface active agents described above,polyoxyethylene fatty acid esters, lignin sulfonic acid salts, abieticacid salts, dinaphthylmethanedisulfonic acid salts, and vegetable oils,such as crop oil concentrate, soybean oil, corn oil, cotton seed oil andsunflower oil.

The herbicide composition of the invention containing, as an activeingredient, a substituted pyrazole derivative represented by theaforesaid formula (I) has a wide herbicidal spectrum, can be applied ina small dose and shows sufficient safety to certain important crops suchas rice, wheat and soybeans.

EXAMPLE

The present invention is further described with reference to thefollowing formulation examples and test examples, but it should beunderstood that the invention is in no way limited by or to thoseexamples. In the following description, the term “part(s)” means“part(s) by weight”.

As the control chemical, a compound of the following formula (V) wasused.

Formulation Example 1

Wettable Powder Composition

50 Parts of each compound shown in Table 2 (Compound No. 1 to 47), 20parts of diatomaceous earth, 22 parts of clay, 3 parts of white carbon,2 parts of lignin sulfonic acid soda and 3 parts ofalkylnaphthalenesulfonic acid soda were mixed and pulverized to obtain awettable powder composition containing 50% by weight of an activeingredient. The control chemical was subjected to the same procedures asdescribed above to obtain a wettable powder composition.

Formulation Example 2

Granule Composition

0.35 Part of each compound shown in Table 2 (Compound No. 1 to 47), 25parts of bentonite, 70.65 parts of talc, 2 parts ofdodecylbenzenesulfonic acid soda and 2 parts of lignin sulfonic acidsoda were mixed. To the mixture, about 20 parts of water was added. Theresulting mixture was kneaded by a kneader, granulated by a granulatorand then subjected to drying and sieving to obtain a granule compositioncontaining 0.35% by weight of an active ingredient. The control chemicalwas subjected to the same procedures as described above to obtain agranule composition.

Test examples of the herbicidal effects exerted by the herbicidecompositions of the invention are given below, but it should beunderstood that the invention is in no way limited by or to those testexamples.

The test results were evaluated according to the following criteria.

Evaluation Criteria

Index: 0-5

5: herbicidal effect of not less than 90% by weight

4: herbicidal effect of not less than 70% by weight and less than 90% byweight

3: herbicidal effect of not less than 50% by weight and less than 70% byweight

2: herbicidal effect of not less than 30% by weight and less than 50% byweight

1: herbicidal effect of not less than 10% by weight and less than 30% byweight

0: herbicidal effect of not less than 0% by weight and less than 10% byweight

In the above evaluation criteria, the term “herbicidal effect” meansevaluation to the objective weeds, and a higher index of the evaluationcriteria means higher herbicidal effect on the objective weeds. On theother hand, a lower index of the evaluation criteria for the crops meanshigher safety to the crops.

Test Example 1

Upland Field Foliage Treatment

A plastic pot of 130 cm² was filled with upland soil. Then, seeds ofweeds, namely, Setaria viridis, Digitaria adscendens, Chenopodium albumand Stellaria media, and seeds of crops, namely, soybean (Glycine max)and wheat (Triticum aestivum), were sowed and covered with soil of about1 cm thick.

On the 14th day after the sowing, a wettable powder composition wasprepared in accordance with Formulation Example 1, diluted with water insuch an amount that the amount of the active ingredient became 1 kg perhectare, and then uniformly applied to the plant leaf surfaces.

On the 21st day after the application, observation and evaluation werecarried out according to the aforesaid criteria.

The results are set forth in Table 3.

Test Example 2

Upland Soil Treatment

A plastic pot of 130 cm² was filled with upland soil. Then, seeds ofweeds, namely, Setaria viridis, Digitaria adscendens, Chenopodium albumand Stellaria media, and seeds of crops, namely, soybean (Glycine max)and wheat (Triticum aestivum), were sowed and covered with soil of about1 cm thick.

On the next day after the sowing, a wettable powder composition wasprepared in accordance with Formulation Example 1, diluted with water insuch an amount that the amount of the active ingredient became 1 kg perhectare, and then uniformly applied to the soil surface.

On the 21st day after the application, observation and evaluation werecarried out according to the aforesaid criteria.

The results are set forth in Table 4.

Test Example 3

Paddy Field Treatment

A plastic pot of 130 cm² was filled with paddy soil, and soil puddlingwas carried out to adjust the submerged depth to 4 cm. Then, seeds ofEchinochloa crusgalli, Monochoria vaginalis, Ammannia multiflora andScirpus juncoides were sowed, and rice (Oryza sative, variety:Koshihikari) of two-leaf period was transplanted by 2 rice plants of 1stub per pot at a depth of 3 cm. On the 10th day after thetransplantation, a wettable powder composition was prepared inaccordance with Formulation Example 1, diluted with water in such anamount that the amount of the active ingredient became 1 kg per hectare,and then dropped to diffuse on the water surface.

On the 21st day after the dropping, observation and evaluation werecarried out according to the aforesaid criteria.

The results are set forth in Table 5.

TABLE 3 Herbicidal activity Compound No. Setaria viridis Digitariaadscendens Chenopodium album Stellaria media Glycine max Triticumaestivum  1 5 5 5 5 1 1  2 4 4 4 4 0 0  3 5 4 5 5 0 0  4 4 4 5 4 0 0  54 4 5 4 0 0  6 4 4 4 4 0 0  7 4 4 5 5 0 0  8 4 5 5 5 0 0  9 4 4 4 4 0 010 4 4 4 4 0 0 11 4 4 4 4 0 0 12 4 5 5 5 1 0 13 5 5 5 5 0 0 14 5 5 5 5 00 15 5 5 5 5 1 0 16 5 5 5 5 1 0 17 5 4 5 5 0 0 18 4 5 5 5 0 0 19 4 5 5 40 0 20 4 4 5 5 0 0 21 4 5 5 5 1 0 22 4 5 5 5 0 0 23 4 4 4 5 0 0 24 4 4 44 0 0 25 4 4 4 4 0 0 26 4 5 5 5 1 0 27 4 5 5 5 0 0 28 4 4 5 5 0 0 29 4 55 5 1 1 30 4 5 5 5 1 0 31 5 5 5 5 1 1 32 4 4 4 4 0 0 33 4 5 5 5 0 0 34 45 5 4 1 1 35 4 4 4 4 0 0 36 5 4 5 5 1 1 37 4 4 5 5 0 0 38 4 4 5 5 1 0 394 4 5 5 1 0 40 4 4 4 4 0 0 41 4 4 4 4 0 0 42 4 4 4 4 0 0 43 4 4 5 5 0 044 4 4 4 4 0 0 45 4 4 5 5 1 0 46 4 4 5 5 1 0 47 3 3 4 4 0 0 Control 0 00 0 0 0

TABLE 4 Herbicidal activity Compound No. Setaria viridis Digitariaadscendens Chenopodium album Stellaria media Glycine max Triticumaestivum  1 4 5 4 4 0 0  2 4 4 4 4 0 0  3 4 4 4 4 0 0  4 4 4 4 4 0 0  54 5 4 4 0 0  6 4 4 4 4 0 0  7 5 4 4 4 0 0  8 4 4 4 4 0 0  9 4 4 5 4 0 010 4 5 4 4 0 0 11 4 4 4 4 0 0 12 4 5 5 4 0 0 13 5 5 5 5 0 0 14 5 5 5 5 00 15 5 5 5 5 0 0 16 5 5 4 5 0 0 17 4 4 4 4 0 0 18 4 5 5 5 0 0 19 4 5 4 50 0 20 4 4 5 4 0 0 21 4 4 4 4 0 0 22 5 5 5 5 0 0 23 4 4 4 4 0 0 24 4 4 44 0 0 25 4 4 4 4 0 0 26 4 4 4 4 0 0 27 4 5 4 5 0 0 28 4 4 4 4 0 0 29 4 44 4 0 0 30 5 5 4 4 0 0 31 5 5 5 5 0 0 32 4 4 4 4 0 0 33 4 4 4 4 0 0 34 44 4 4 0 0 35 4 4 4 4 0 0 36 4 4 4 4 0 0 37 5 5 4 5 0 0 38 4 4 4 4 0 0 394 4 4 4 0 0 40 4 4 4 4 0 0 41 4 4 4 4 0 0 42 4 4 4 4 0 0 43 4 4 4 4 0 044 4 4 4 4 0 0 45 4 4 4 4 0 0 46 4 4 4 4 0 0 47 4 4 4 3 0 0 Control 0 00 0 0 0

TABLE 5 Herbicidal activity Compound No. Echinochloa spp. Scirpusjuncoides Monochoria vaginalis Ammannia multiflora Oryza sativa  1 5 5 54 1  2 3 3 3 3 0  3 3 3 4 4 0  4 4 4 5 3 0  5 P 3 5 3 0  6 4 3 3 3 0  74 3 4 4 0  8 4 4 5 5 0  9 3 3 3 3 0 10 3 3 3 3 0 11 3 3 3 3 0 12 4 4 5 50 13 5 5 5 5 0 14 5 5 5 5 0 15 5 5 5 5 0 16 5 5 5 5 0 17 5 4 5 5 0 18 55 5 5 1 19 5 5 5 5 1 20 4 4 5 5 0 21 5 4 5 5 0 22 5 5 5 5 1 23 3 3 4 5 024 4 3 3 3 0 25 3 3 3 3 0 26 5 4 5 5 0 27 5 5 5 5 1 28 5 5 5 5 1 29 4 45 5 0 30 4 4 5 5 0 31 5 5 5 5 1 32 3 3 3 3 0 33 5 5 5 5 1 34 3 3 5 3 035 3 3 4 4 0 36 3 3 3 3 0 37 3 3 3 3 0 38 3 3 4 3 0 39 4 4 3 3 0 40 3 33 3 0 41 4 3 3 3 0 42 3 3 3 3 0 43 3 4 3 3 0 44 3 3 3 3 0 45 4 4 5 4 046 3 3 3 3 0 47 3 3 2 2 0 Control 0 0 0 0 0

What is claimed is:
 1. A method of exerting a herbicidal effect on algaeor weeds comprising applying a herbicide composition to algae or weeds,the herbicide composition containing, as an active ingredient, one ormore substituted pyrazole derivatives represented by the followingformula (I):

wherein X is R¹OOC, R¹HNOC, R¹R¹NOC, a cyano group or a 5-membered or6-membered aromatic heterocyclic group, W is an alkylene group of 1 to 3carbon atoms or NR¹, R is a lower alkyl group of 1 to 4 carbon atoms ora lower haloalkyl group of 1 to 4 carbon atoms, A, B and D may be thesame or different and are each a hydrogen atom, a halogen atom or agroup selected from the group consisting of R¹, R¹O, R¹S, R¹SO, R¹SO₂,(R¹)₂N, R¹OOC, ROR², R¹ON═CH, a cyano group, a nitro group, a loweralkenyl group of 2 to 4 carbon atoms, a lower alkynyl group of 2 to 4carbon atoms, a cycloalkyl group of 3 to 7 carbon atoms, Ph, PhCH₂, PhO,PhCH₂O, PhOR², PhS, PhCH₂S, PhSR², PhCH₂ON═CH, Naph and Het, with theproviso that there is no case where A, B and D are hydrogen atoms at thesame time and there is no case where A, B and D are aromatic groups oraromatic heterocyclic groups at the same time, R¹ is a lower alkyl groupof 1 to 4 carbon atoms or a lower haloalkyl group of 1 to 4 carbonatoms, R² is a lower alkylene group of 1 to 4 carbon atoms, Ph is anunsubstituted or substituted phenyl group, Naph is an unsubstituted orsubstituted naphthyl group, and Het is an unsubstituted or substituted,5-membered or 6-membered aromatic heterocyclic group.
 2. The method asclaimed in claim 1, wherein the substituted pyrazole derivative is asubstituted pyrazole derivative of the formula (I) wherein X is R¹OOC, Wis a methylene group or an ethylene group, R is a methyl group, A and Bare each a hydrogen atom, a halogen atom, R¹ or R¹S, and D is Ph.
 3. Themethod as claimed in claim 1, wherein the substituted pyrazolederivative represented by the formula (I) is at least one compoundselected from the group consisting of: a substituted pyrazole derivative(compound No. 1) wherein A and B are each a hydrogen atom, D is a phenylgroup, W is a methylene group, X is a methoxycarbonyl group, and R is amethyl group, a substituted pyrazole derivative (compound No. 2) whereinA is a methyl group, B is a hydrogen atom, D is a phenyl group, W is amethylene group, X is a methoxycarbonyl group, and R is a methyl group,a substituted pyrazole derivative (compound No. 3) wherein A is a methylgroup, B is a hydrogen atom, D is a 3-methylphenyl group, W is amethylene group, X is a methoxycarbonyl group, and R is a methyl group,a substituted pyrazole derivative (compound No. 4) wherein A is a methylgroup, B is a hydrogen atom, D is a 2-chlorophenyl group, W is amethylene group, X is a methoxycarbonyl group, and R is a methyl group,a substituted pyrazole derivative (compound No. 5) wherein A is a methylgroup, B is a hydrogen atom, D is a 2,5-dimethylphenyl group, W is amethylene group, X is a methoxycarbonyl group, and R is a methyl group,a substituted pyrazole derivative (compound No. 6) wherein A is a methylgroup, B is a hydrogen atom, D is a 2,3-dichlorophenyl group, W is amethylene group, X is a methoxycarbonyl group, and R is a methyl group,a substituted pyrazole derivative (compound No. 7) wherein A is a methylgroup, B is a hydrogen atom, D is a 2,4-dichlorophenyl group, W is amethylene group, X is a methoxycarbonyl group, and R is a methyl group,a substituted pyrazole derivative (compound No. 8) wherein A is a methylgroup, B is a hydrogen atom, D is a 2,5-dichlorophenyl group, W is amethylene group, X is a methoxycarbonyl group, and R is a methyl group,a substituted pyrazole derivative (compound No. 9) wherein A is a methylgroup, B is a hydrogen atom, D is a 2,6-dichlorophenyl group, W is amethylene group, X is a methoxycarbonyl group, and R is a methyl group,a substituted pyrazole derivative (compound No. 10) wherein A is amethyl group, B is a hydrogen atom, D is a 3,4-dichlorophenyl group, Wis a methylene group, X is a methoxycarbonyl group, and R is a methylgroup, a substituted pyrazole derivative (compound No. 11) wherein A isa methyl group, B is a hydrogen atom, D is a 3,5-dichlorophenyl group, Wis a methylene group, X is a methoxycarbonyl group, and R is a methylgroup, a substituted pyrazole derivative (compound No. 12) wherein A isa methyl group, B is a chlorine atom, D is a phenyl group, W is amethylene group, X is a methoxycarbonyl group, and R is a methyl group,a substituted pyrazole derivative (compound No. 13) wherein A is ahydrogen atom, B is a methyl group, D is a phenyl group, W is amethylene group, X is a methoxycarbonyl group, and R is a methyl group,a substituted pyrazole derivative (compound No. 14) wherein A is ahydrogen atom, B is a methyl group, D is a 4-fluorophenyl group, W is amethylene group, X is a methoxycarbonyl group, and R is a methyl group,a substituted pyrazole derivative (compound No. 15) wherein A is ahydrogen atom, B is a chlorine atom, D is a phenyl group, W is amethylene group, X is a methoxycarbonyl group, and R is a methyl group,a substituted pyrazole derivative (compound No. 16) wherein A is ahydrogen atom, B is a chlorine atom, D is a 3-methoxyphenyl group, W isa methylene group, X is a methoxycarbonyl group, and R is a methylgroup, a substituted pyrazole derivative (compound No. 17) wherein A isa methyl group, B is a chlorine atom, D is a 3-methylphenyl group, W isa methylene group, X is a methoxycarbonyl group, and R is a methylgroup, a substituted pyrazole derivative (compound No. 18) wherein A isa methyl group, B is a chlorine atom, D is a 2-chlorophenyl group, W isa methylene group, X is a methoxycarbonyl group, and R is a methylgroup, a substituted pyrazole derivative (compound No. 19) wherein A isa methyl group, B is a chlorine atom, D is a 2,5-dimethylphenyl group, Wis a methylene group, X is a methoxycarbonyl group, and R is a methylgroup, a substituted pyrazole derivative (compound No. 20) wherein A isa methyl group, B is a chlorine atom, D is a 2,3-dichlorophenyl group, Wis a methylene group, X is a methoxycarbonyl group, and R is a methylgroup, a substituted pyrazole derivative (compound No. 21) wherein A isa methyl group, B is a chlorine atom, D is a 2,4-dichlorophenyl group, Wis a methylene group, X is a methoxycarbonyl group, and R is a methylgroup, a substituted pyrazole derivative (compound No. 22) wherein A isa methyl group, B is a chlorine atom, D is a 2,5-dichlorophenyl group, Wis a methylene group, X is a methoxycarbonyl group, and R is a methylgroup, a substituted pyrazole derivative (compound No. 23) wherein A isa methyl group, B is a chlorine atom, D is a 2,6-dichlorophenyl group, Wis a methylene group, X is a methoxycarbonyl group, and R is a methylgroup, a substituted pyrazole derivative (compound No. 24) wherein A isa methyl group, B is a chlorine atom, D is a 3,4-dichlorophenyl group, Wis a methylene group, X is a methoxycarbonyl group, and R is a methylgroup, a substituted pyrazole derivative (compound No. 25) wherein A isa methyl group, B is a chlorine atom, D is a 3,5-dichlorophenyl group, Wis a methylene group, X is a methoxycarbonyl group, and R is a methylgroup, a substituted pyrazole derivative (compound No. 26) wherein A isa methyl group, B is a bromine atom, D is a 3-methylphenyl group, W is amethylene group, X is a methoxycarbonyl group, and R is a methyl group,a substituted pyrazole derivative (compound No. 27) wherein A is amethyl group, B is a bromine atom, D is a 2-chlorophenyl group, W is amethylene group, X is a methoxycarbonyl group, and R is a methyl group,a substituted pyrazole derivative (compound No. 28) wherein A is amethyl group, B is a bromine atom, D is a 2,5-dimethylphenyl group, W isa methylene group, X is a methoxycarbonyl group, and R is a methylgroup, a substituted pyrazole derivative (compound No. 29) wherein A isa methyl group, B is a bromine atom, D is a 2,3-dichlorophenyl group, Wis a methylene group, X is a methoxycarbonyl group, and R is a methylgroup, a substituted pyrazole derivative (compound No. 30) wherein A isa methyl group, B is a bromine atom, D is a 2,4-dichlorophenyl group, Wis a methylene group, X is a methoxycarbonyl group, and R is a methylgroup, a substituted pyrazole derivative (compound No. 31) wherein A isa methyl group, B is a bromine atom, D is a 2,5-dichlorophenyl group, Wis a methylene group, X is a methoxycarbonyl group, and R is a methylgroup, a substituted pyrazole derivative (compound No. 32) wherein A isa methyl group, B is a bromine atom, D is a 3,5-dichlorophenyl group, Wis a methylene group, X is a methoxycarbonyl group, and R is a methylgroup, a substituted pyrazole derivative (compound No. 33) wherein A isa methyl group, B is a methyl group, D is a phenyl group, W is amethylene group, X is a methoxycarbonyl group, and R is a methyl group,a substituted pyrazole derivative (compound No. 34) wherein A is amethyl group, B is a methyl group, D is a 3-chlorophenyl group, W is amethylene group, X is a methoxycarbonyl group, and R is a methyl group,a substituted pyrazole derivative (compound No. 35) wherein A is amethyl group, B is a methyl group, D is a 4-chlorophenyl group, W is amethylene group, X is a methoxycarbonyl group, and R is a methyl group,a substituted pyrazole derivative (compound No. 36) wherein A is anethyl group, B is a hydrogen atom, D is a phenyl group, W is a methylenegroup, X is a methoxycarbonyl group, and R is a methyl group, asubstituted pyrazole derivative (compound No. 37) wherein A is amethylthio group, B is a hydrogen atom, D is a phenyl group, W is amethylene group, X is a methoxycarbonyl group, and R is a methyl group,a substituted pyrazole derivative (compound No. 38) wherein A is amethylthio group, B is a hydrogen atom, D is a 3-chlorophenyl group, Wis a methylene group, X is a methoxycarbonyl group, and R is a methylgroup, a substituted pyrazole derivative (compound No. 39) wherein A isan ethyl group, B is a chlorine atom, D is a phenyl group, W is amethylene group, X is a methoxycarbonyl group, and R is a methyl group,a substituted pyrazole derivative (compound No. 40) wherein A is apropyl group, B is a chlorine atom, D is a 3-chlorophenyl group, W is amethylene group, X is a methoxycarbonyl group, and R is a methyl group,a substituted pyrazole derivative (compound No. 41) wherein A is amethylthio group, B is a chlorine atom, D is a phenyl group, W is amethylene group, X is a methoxycarbonyl group, and R is a methyl group,a substituted pyrazole derivative (compound No. 42) wherein A is amethylthio group, B is a chlorine atom, D is a 3-chlorophenyl group, Wis a methylene group, X is a methoxycarbonyl group, and R is a methylgroup, a substituted pyrazole derivative (compound No. 43) wherein A isan ethyl group, B is a bromine atom, D is a phenyl group, W is amethylene group, X is a methoxycarbonyl group, and R is a methyl group,a substituted pyrazole derivative (compound No. 44) wherein A is amethylthio group, B is a bromine atom, D is a phenyl group, W is amethylene group, X is a methoxycarbonyl group, and R is a methyl group,a substituted pyrazole derivative (compound No. 45) wherein A is achlorine atom, B is a methyl group, D is a phenyl group, W is amethylene group, X is a methoxycarbonyl group, and R is a methyl group,a substituted pyrazole derivative (compound No. 46) wherein A is abromine atom, B is a methyl group, D is a phenyl group, W is a methylenegroup, X is a methoxycarbonyl group, and R is a methyl group, and asubstituted pyrazole derivative (compound No. 47) wherein A is ahydrogen atom, B is a methyl group, D is a phenyl group, W is anethylene group, X is a methoxycarbonyl group, and R is a methyl group.